CN110559997A - Cement-based adsorbent and preparation method and application thereof - Google Patents
Cement-based adsorbent and preparation method and application thereof Download PDFInfo
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- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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Abstract
The invention provides a cement-based adsorbent and a preparation method and application thereof, belonging to the field of adsorbent preparation. The cement-based adsorbent provided by the invention is prepared from the following components in parts by weight: 8-15 parts of cement, 5-12 parts of fly ash powder, 1.5-16 parts of calcium hydroxide, 0.1-2 parts of graphene oxide powder, 0.5-3 parts of polycarboxylic acid water reducing agent, 0.3-1 part of foaming agent and 25-87 parts of water. The added graphene oxide contains a large number of oxygen-containing functional groups on the surface, and can be complexed with heavy metal ions, the added calcium hydroxide solution modifies the fly ash, so that the surface activity of the fly ash is increased, the adsorption efficiency of the cement-based adsorbent on high-concentration heavy metal ions is improved, the modified fly ash and graphene oxide can improve the pore structure of the cement-based adsorbent, the porosity of the cement-based adsorbent is reduced, and the strength, the toughness and the durability of the cement-based adsorbent are effectively improved.
Description
Technical Field
the invention relates to the field of preparation of adsorbents, and particularly relates to a cement-based adsorbent and a preparation method and application thereof.
Background
Copper ions are a common heavy metal contaminant, mainly from the waste water of mining, smelting and metal processing of metal ores, machine manufacturing, organic synthesis and other industries. Copper ion pollution generally has the characteristics of high toxicity, difficult degradation and long-term persistence, and can finally enter human organs through food chains after biological enrichment. Copper is an essential element required by a human body, but if the copper exceeds the required amount of the human body by 100-150 times, liver tissue necrosis, kidney damage, hemolysis and the like can be caused. Therefore, the treatment of copper ion contamination has become more and more important.
The cement has the characteristics of low cost, high durability and the like, is widely applied to construction projects, and almost all wastewater collection and conveying channels and treatment structures take the wastewater as main materials. Although cement contains a large amount of Si-O-Si bonds, Al-O-Al bonds and-OH, adsorption and chelate complexes of dipole-dipole bonds with various metals can be generated, and heavy metal sewage can be treated. However, the adsorption time of cement to heavy metal ions is too long, so that the adsorption effect is general, and the application and popularization of the cement are restricted.
disclosure of Invention
In view of the above, the invention provides a cement-based adsorbent, and a preparation method and an application thereof, and the cement-based adsorbent provided by the invention has good adsorption performance, and can effectively shorten the time for the cement-based adsorbent to adsorb high-concentration heavy metal ions.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a cement-based adsorbent which is prepared from the following components in parts by weight:
8-15 parts of cement, 5-12 parts of fly ash powder, 1.5-16 parts of calcium hydroxide, 0.1-2 parts of graphene oxide powder, 0.5-3 parts of polycarboxylic acid water reducing agent, 0.3-1 part of foaming agent and 25-87 parts of water.
Preferably, the fly ash powder has a particle size < 200 mesh.
Preferably, the particle size of the graphene oxide powder is <120 meshes.
Preferably, the active content of the foaming agent is more than or equal to 30 percent.
preferably, the Ca (OH)2The calcium hydroxide solution is added in a form of calcium hydroxide solution, and the molar concentration of the calcium hydroxide solution is 1-3 moL/L.
The invention also provides a preparation method of the cement-based adsorbent in the technical scheme, which comprises the following steps:
Mixing fly ash powder with Ca (OH)2Mixing the solutions, and carrying out modification reaction to obtain modified fly ash;
and mixing the modified fly ash, the graphene oxide powder, the polycarboxylic acid water reducing agent, the cement, the foaming agent and water, and then maintaining to obtain the cement-based adsorbent.
Preferably, the temperature of the modification reaction is 80-100 ℃ and the time is 30-60 min.
preferably, the curing temperature is 18-22 ℃, the relative humidity is greater than or equal to 95 ℃, and the curing time is 3-7 days.
The invention also provides the application of the cement-based adsorbent in the technical scheme or the cement-based adsorbent prepared by the preparation method in the technical scheme in treating copper ion-containing solution.
Preferably, the pH value of the copper ion-containing solution is 2-8, and the concentration of copper ions is 50-500 mg/L.
The invention provides a cement-based adsorbent which is prepared from the following components in parts by weight: 8-15 parts of cement, 5-12 parts of fly ash powder, 1.5-16 parts of calcium hydroxide, 0.1-2 parts of graphene oxide powder, 0.5-3 parts of polycarboxylic acid water reducing agent, 0.3-1 part of foaming agent and 25-87 parts of water. In the invention, the surface of the graphene oxide contains a large number of oxygen-containing functional groups (hydroxyl, carboxyl and epoxy functional groups), and the oxygen-containing functional groups can perform a complex reaction with heavy metal ions, so that the effective adsorption of the heavy metal ions by the cement-based adsorbent is realized; the fly ash is modified by adding calcium hydroxide, Si-O-Si and Si-O-Al network structures in the fly ash are destroyed and depolymerized, so that the surface activity of the fly ash is increased, the surface of the modified fly ash is negatively charged, the fly ash can be combined with heavy metal ions with positive charges through electrostatic action, and simultaneously, new active sites of ≡ SiO-and ═ AlO-are generated, the complex reaction can be carried out with the heavy metal ions, the aim of removing the heavy metal ions in the solution is fulfilled, the adsorption efficiency of the cement-based adsorbent is effectively improved, and the adsorption time is shortened. The modified fly ash and graphene oxide can improve the pore structure of the cement-based adsorbent, reduce the pore diameter, promote the growth of hydrated crystals at the holes and cracks of the cement-based adsorbent, repair the defects through growth and aggregation, reduce the porosity, ensure that the cement-based adsorbent is dense and uniform, have the effects of improving the strength and toughness, and effectively improve the durability of the cement adsorbent so as to facilitate the separation of the cement-based adsorbent. The embodiment result shows that after the cement-based adsorbent provided by the invention adsorbs high-concentration copper ions in a solution for 2 hours, the final equilibrium adsorption rate of the cement-based adsorbent on the copper ions in the solution can reach 96.858-99.587%, the adsorption amount is 7.942-25.9548 mg/g, the breaking strength is 7.61-8.78 MPa, and the compressive strength is 41.65-48.35 MPa.
Meanwhile, the cement-based adsorbent provided by the invention reasonably utilizes the fly ash, has low cost, can realize the purpose of treating wastes with wastes, and provides a new way for the utilization of fly ash resources.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an SEM image of cement;
Fig. 2 is an SEM image of the cement-based adsorbent prepared in example 1, wherein a is an SEM image of the cement-based adsorbent at 5000 times, b is an SEM image of the cement-based adsorbent at 10000 times, and c is an SEM image of the cement-based adsorbent at 20000 times;
FIG. 3 is a FT-IR spectrum of the cement-based sorbent, fly ash, cement and graphene oxide prepared in example 2;
FIG. 4 is a graph showing the adsorption effect of the cement-based adsorbent prepared in example 3 on copper ions as a function of adsorption time;
FIG. 5 is a graph showing the effect of the cement-based adsorbent prepared in example 3 on the adsorption of copper ions as a function of temperature;
FIG. 6 is a graph of the adsorption isotherm of copper ions by the cement-based adsorbent prepared in example 3;
fig. 7 is a graph showing the relationship between the adsorption effect of the cement-based adsorbent prepared in example 3 on copper ions and pH.
Detailed Description
The invention provides a cement-based adsorbent which is prepared from the following components in parts by weight:
8-15 parts of cement, 5-12 parts of fly ash powder, 1.5-16 parts of calcium hydroxide, 0.1-2 parts of graphene oxide powder, 0.5-3 parts of polycarboxylic acid water reducing agent, 0.3-1 part of foaming agent and 25-87 parts of water.
the invention provides a cement-based adsorbent, which comprises 8-15 parts of cement, and preferably 9-11 parts of cement. In the invention, the cement is preferably Portland cement, and the particle size of the cement is preferably 80-100 meshes.
The cement-based adsorbent comprises 5-12 parts of fly ash powder by weight of cement, and preferably 7-9 parts. In the invention, the particle size of the fly ash powder is preferably less than 200 meshes, and more preferably 80-100 meshes.
Based on the weight parts of the cement, the cement-based adsorbent comprises 1.5-16 parts of calcium hydroxide, and more preferably 5-9 parts of calcium hydroxide. In the present invention, the calcium hydroxide is preferably Ca (OH)2The calcium hydroxide solution is added in the form of solution, and the molar concentration of the calcium hydroxide solution is preferably 1-3 moL/L, and more preferably 2-2.5 moL/L. The invention adds Ca (OH)2The solution and the fly ash powder generate modification reaction to destroy and depolymerize Si-O-Si and Si-O-Al network structures in the fly ash, so that the surface activity of the fly ash is increased, the surface of the modified fly ash has negative charges, the modified fly ash can be combined with heavy metal ions with positive charges through electrostatic action, and simultaneously, new active sites of ≡ SiO-and ═ AlO-are generated, the complex reaction can be generated with the heavy metal ions, the aim of removing the heavy metal ions in the solution is fulfilled, and the adsorption of the cement-based adsorbent to the high-concentration heavy metal ions is effectively improvedThe adsorption efficiency is improved, and the adsorption time is shortened. The modified fly ash and graphene oxide can improve the pore structure of the cement-based adsorbent, reduce the pore diameter, promote hydrated crystals to grow at the holes and cracks of the cement-based adsorbent, repair defects through growth and aggregation, reduce the porosity, enable the cement-based adsorbent to be dense and uniform, effectively improve the strength, toughness and durability of the cement adsorbent, and facilitate the separation of the cement-based adsorbent.
The cement-based adsorbent comprises 0.1-2 parts by weight of graphene oxide powder, and more preferably 0.5-1.5 parts by weight of cement. In the present invention, the particle size of the graphene oxide powder is <120 mesh, and more preferably 80 to 100 mesh. The surface of the added graphene oxide contains a large number of oxygen-containing functional groups (hydroxyl, carboxyl and epoxy functional groups) and can generate a complex reaction with heavy metal ions, so that the effective adsorption of the cement-based adsorbent to the heavy metal ions is realized.
Based on the weight parts of the cement, the cement-based adsorbent comprises 0.5-3 parts of polycarboxylic acid water reducing agent, and preferably 1-2 parts. In the invention, the polycarboxylate superplasticizer is preferably a polyester polycarboxylate superplasticizer or a polyether polycarboxylate superplasticizer, the polycarboxylate superplasticizer is preferably added in the form of a solution, the water reducing rate of the polycarboxylate superplasticizer solution is preferably more than 20%, more preferably 25-30%, the solid content is preferably 20-40%, and the pH value is preferably 7.0-8.0. In the embodiment of the invention, the PCAQ8081 polycarboxylate water reducer is further preferable.
The cement-based adsorbent comprises 0.3-1 part by weight of foaming agent, and more preferably 0.5-0.6 part by weight of cement. In the present invention, the active content of the foaming agent is preferably not less than 30%, and more preferably 35% to 40%. In the present invention, the foaming agent is preferably a liquid foaming agent including sodium dodecylbenzenesulfonate, rosin soap foaming agent or saponin-type foaming agent. Sodium dodecylbenzenesulfonate solution is further preferred in the present examples. According to the invention, the foaming agent is added to enable the interior of the raw material mixture to be full of bubbles, and the interior of the formed cement adsorbent is porous and rough, so that the adsorption efficiency of the cement-based adsorbent on high-concentration heavy metal ions is improved.
The cement-based adsorbent comprises 25-87 parts of water, preferably 44-56 parts of water based on the weight of the cement. In the present invention, the water is preferably distilled water.
The concrete source of the cement-based adsorbent raw material is not particularly limited in the invention, and the cement-based adsorbent raw material can be prepared from conventional commercial products in the field.
The invention also provides a preparation method of the cement-based adsorbent in the technical scheme, which comprises the following steps:
Mixing fly ash powder with Ca (OH)2Mixing the solutions, and carrying out modification reaction to obtain modified fly ash;
And mixing the modified fly ash, the graphene oxide powder, the polycarboxylic acid water reducing agent, the cement, the foaming agent and water, and then maintaining to obtain the cement-based adsorbent.
The fly ash powder is preferably ball-milled and then mixed with Ca (OH)2the solutions were mixed. In the invention, the ball milling is preferably carried out in a ball mill, and the speed of the ball milling is preferably 250-350 r/min, and more preferably 300 r/min; the time of the ball milling is preferably 2 hours, and the particle size after the ball milling is preferably 80 meshes. The present invention is not particularly limited to the specific mixing operation, and the mixing method known to those skilled in the art may be used. According to the invention, the glass structure of the fly ash powder can be destroyed by ball milling the fly ash powder, the specific surface area of the fly ash powder is increased, and the fly ash modification is facilitated.
in the present invention, the fly ash powder is mixed with Ca (OH)2The amount ratio of the solution is preferably 1 g: 4 mL-1 g: 6mL, more preferably 1 g: 5 mL. In the present invention, the mixing is preferably carried out in a water bath. In the present invention, the mixing is preferably performed by stirring; the stirring speed is preferably 200-300 r/min, and more preferably 300 r/min; the stirring time is preferably 30 min.
In the invention, the temperature of the modification reaction is preferably 80-100 ℃, and more preferably 90 ℃; the time of the modification reaction is preferably 30-60 min, and more preferably 30 min.
After the modification reaction is finished, the obtained modified product is preferably subjected to centrifugal separation, water washing, drying and grinding in sequence. The invention has no special limitation on the washing times, and the pH value of the washing product can be washed to be neutral. In the present invention, the particle size after grinding is preferably 80 to 120 mesh. The present invention is not particularly limited to the specific operations of the centrifugation, water washing, drying and grinding, and the centrifugation, water washing, drying and grinding methods known to those skilled in the art may be used.
After the modified fly ash is obtained, the modified fly ash, the graphene oxide powder, the polycarboxylic acid water reducing agent, the cement, the foaming agent and the water are mixed and then maintained, so that the cement-based adsorbent is obtained.
in the invention, the mixing mode is preferably that graphene oxide powder is sequentially subjected to first mixing with water and a polycarboxylate superplasticizer to obtain a graphene oxide/polycarboxylate superplasticizer mixed solution, and then cement is sequentially subjected to second mixing with modified fly ash, a part of graphene oxide/polycarboxylate superplasticizer mixed solution, a foaming agent and the rest of graphene oxide/polycarboxylate superplasticizer mixed solution.
According to the invention, the graphene oxide powder is preferably subjected to ultrasonic treatment in distilled water to obtain a graphene oxide suspension. In the invention, the power of ultrasonic treatment is preferably 200-300W, and the time is preferably 1-2 h. In the present invention, the mass ratio of the graphene oxide powder to distilled water is preferably 1: 100. The invention improves the dispersibility of the graphene oxide in the distilled water through ultrasonic treatment.
According to the invention, the graphene oxide suspension and the polycarboxylic acid water reducing agent are preferably subjected to first mixing to obtain a graphene oxide/polycarboxylic acid water reducing agent mixed solution. In the invention, the first mixing mode is preferably stirring, the stirring speed is preferably 150 to 300r/min, more preferably 200r/min, the time is preferably 20 to 40min, and the temperature is preferably 40 to 60 ℃, more preferably 50 ℃.
According to the invention, after cement and modified fly ash are preferably mixed, the mixture is sequentially mixed with a part of graphene oxide/polycarboxylate superplasticizer mixed solution, a foaming agent and the rest of graphene oxide/polycarboxylate superplasticizer mixed solution for the second mixing, and then maintenance is carried out.
In the present invention, the second mixing mode is preferably stirring, the stirring speed is preferably 20 to 40r/min, more preferably 30r/min, and the time is preferably 1 to 2 min. In the invention, the volume ratio of the partial graphene oxide/polycarboxylate superplasticizer mixed solution to the residual graphene oxide/polycarboxylate superplasticizer mixed solution is preferably 1: 4-3: 2, and more preferably 1: 1. Because the graphene oxide is easy to generate flocculation reaction under the alkaline condition, the concentration of the graphene oxide in a reaction system is controlled by adding the graphene oxide/polycarboxylate superplasticizer mixed solution twice, so that the flocculation reaction is avoided, and the graphene oxide, the cement and the fly ash are fully combined.
After the mixing is finished, the obtained mixture is preferably stirred for 1-2 min at the rotating speed of 20-40 r/min, stopped for 2-3 min, stirred for 5-6 min at the rotating speed of 100-150 r/min, sequentially subjected to mold feeding, compaction and leveling, and then maintained. The concrete operations of the mold feeding, the vibrating and the floating are not limited in the invention, and the mold feeding, the vibrating and the floating which are well known to those skilled in the art can be adopted.
In the invention, the curing temperature is preferably 18-22 ℃, and more preferably 20 ℃; the relative humidity of the maintenance is more than or equal to 95 percent, and the preferable range is 98 percent; the curing time is preferably 3 to 7 days, and more preferably 5 days. The concrete operation of the curing is not particularly limited in the present invention, and curing methods known to those skilled in the art can be adopted.
After the maintenance is finished, the maintained product is preferably ground and sieved in sequence to obtain the cement-based adsorbent. In the invention, the particle size after screening is preferably 40-80 meshes. The specific operation of the grinding and sieving is not particularly limited in the present invention, and the grinding and sieving means well known to those skilled in the art may be used.
The invention also provides the application of the cement-based adsorbent in the technical scheme or the cement-based adsorbent prepared by the preparation method in the technical scheme in treating copper ion-containing solution.
In the invention, the pH value of the copper ion-containing solution is preferably 2-8, more preferably 6, and the concentration of copper ions is 50-500 mg/L, more preferably 70-300 mg/L, more preferably 82 mg/L. In the invention, the dosage of the cement-based adsorbent is preferably 5-15 g/L, and more preferably 10 g/L. In the invention, the application is preferably that the cement-based adsorbent is mixed with a copper ion-containing solution, the pH value of the solution is adjusted to about 6, and then the solution is vibrated at room temperature. In the present invention, the mixing temperature is preferably 20 to 80 ℃, and more preferably 20 to 60 ℃. In the invention, the oscillation rate is preferably 150-300 rpm, and more preferably 200-250 rpm; the time of the oscillation is preferably 2 h.
The cement-based adsorbent provided by the present invention, the preparation method and the application thereof will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
example 1
Ball-milling the fly ash on a ball mill for 2 hours at the rotating speed of 300r/min, and then sieving the fly ash with a 80-mesh sieve to obtain fly ash powder; 7g of fly ash powder and 2moL/LCa (OH) of mass concentration2stirring the solution for 30min in a water bath at 90 ℃ at the rotating speed of 300r/min according to the dosage ratio of 1g to 6mL, then carrying out centrifugal separation, washing with water to be neutral, drying, grinding and sieving with a 100-mesh sieve to obtain modified fly ash;
Weighing 0.5g of graphene oxide, adding the graphene oxide into 8mL of distilled water, performing ultrasonic treatment for 2 hours to obtain a uniformly dispersed graphene oxide suspension, mixing the graphene oxide suspension with a 1mLPCAQ8081 polycarboxylate superplasticizer, and stirring for 20 minutes at 40 ℃ at 200r/min to obtain a graphene oxide/polycarboxylate superplasticizer mixed solution;
Weighing 10g of cement and the obtained modified fly ash, sequentially adding 4.5mL of graphene oxide/polycarboxylic acid water reducer mixed solution and 0.5mL of sodium dodecyl benzene sulfonate foaming agent into a stirrer, stirring for 1min at the stirring speed of 30r/min, then adding the rest 4.5mL of graphene oxide/polycarboxylic acid water reducer mixed solution, stirring for 1min at the stirring speed of 30r/min, stopping for 2min, stirring for 5min at the stirring speed of 100r/min, then placing into a mold, compacting, leveling, curing for 5 days at the temperature of 20 ℃ and under the condition that the relative humidity is 95% until forming, finally grinding into powder, and sieving with a 60-mesh sieve to obtain the cement-based adsorbent.
Fig. 1 and 2 are SEM images of cement and cement-based sorbents, respectively. As can be seen from figures 1-2, the cement structure is relatively loose, disorderly, and the hole is many and the hole is big, and cement-based adsorbent surface is coarse, and unsmooth, but the structure is closely knit, and the aperture is little, and the porosity is lower, is porous and network structure, can see that the hydrated crystal grows in hole, the crack department of cement-based adsorbent, reaches the restoration defect through growing and gathering in addition, has the effect that improves intensity and toughness.
Adding 1g of cement-based adsorbent into 100mL of copper ion-containing solution, wherein the concentration of copper ions is 82.409mg/L, adjusting the pH value of the solution to 6 at the constant temperature of 25 +/-0.5 ℃, oscillating (150 revolutions per minute) for 2 hours, and then balancing the adsorption of the cement-based adsorbent on the copper ions in the solution, thereby measuring that the final equilibrium adsorption rate of the cement-based adsorbent on the copper ions in the solution is 96.858% and the adsorption amount is 7.942 mg/g.
Comparative example
The cement-based adsorbent provided by the invention has high adsorption efficiency and short adsorption time by taking conventional commercially available cement in the field as a comparative example.
Grinding 1g of cement block adsorbent made of conventional commercially available cement into powder, sieving with a 60-mesh sieve, adding into 100mL of copper ion-containing solution, wherein the concentration of copper ions is 82.409mg/L, adjusting the pH value of the solution to 6 at a constant temperature of 25 +/-0.5 ℃, oscillating (150 revolutions per minute) for 6 hours, and balancing the adsorption of the cement block adsorbent on the copper ions in the solution to obtain the final equilibrium adsorption rate of the cement block adsorbent on the copper ions in the solution, namely 34.457%, and the adsorption capacity of the cement block adsorbent is 2.825 mg/g.
Example 2
ball-milling the fly ash on a ball mill for 2 hours at the rotating speed of 300r/min, and then sieving the fly ash with a 80-mesh sieve to obtain fly ash powder; 8g of fly ash powder and 3moL/LCa (OH) of mass concentration2Stirring the solution for 30min in a water bath at 90 ℃ at the rotating speed of 300r/min according to the dosage ratio of 1g to 5mL, then carrying out centrifugal separation, washing with water to be neutral, drying, grinding and sieving with a 100-mesh sieve to obtain modified fly ash;
Weighing 1g of graphene oxide, adding the graphene oxide into 10mL of distilled water, performing ultrasonic treatment for 2 hours to obtain a uniformly dispersed graphene oxide suspension, mixing the graphene oxide suspension with a 2mLPCAQ8081 polycarboxylate water reducer, and stirring for 20 minutes at 30 ℃ at 200r/min to obtain a graphene oxide/polycarboxylate water reducer mixed solution;
Weighing 10g of cement and the obtained modified fly ash into a stirrer, sequentially adding 7mL of graphene oxide/polycarboxylic acid water reducer mixed solution and 0.6mL of sodium dodecyl benzene sulfonate foaming agent, stirring for 1min at a stirring speed of 30r/min, then adding the rest 5mL of graphene oxide/polycarboxylic acid water reducer mixed solution, stirring for 1min at a stirring speed of 30r/min, stopping for 2min, stirring for 5min at a stirring speed of 100r/min, then placing into a mold, compacting, leveling, curing for 5 days at 18 ℃ under the condition that the relative humidity is 98% until molding, finally grinding into powder, and sieving with a 60-mesh sieve to obtain the cement-based adsorbent.
FIG. 3 is a FT-IR spectrum of a cement-based adsorbent, which can be found at 3456cm-1And 1633cm-1The peaks at the positions correspond to O-H stretching vibration and C ═ C group stretching vibration caused by hydroxyl groups respectively, the absorption peak wave numbers of the cement-based adsorbents O-H and C ═ C are enhanced compared with other materials, and the absorption peak wave number of the O-H is shifted to the left; 1423cm-1The peak of (A) corresponds to the bending vibration of carboxyl C-OH groups, and compared with cement, the C-OH absorption peak of the cement-based adsorbent is weakened, which is probably caused by the addition of fly ash and graphene oxide; 1086cm-1The peak of (a) corresponds to the stretching vibration of the C-O group, and the C-O absorption peak of the cement-based adsorbent is enhanced compared with that of cement, which is probably caused by the incorporation of the fly ash. The results show that the cement-based adsorbent successfully introduces materials such as fly ash and graphene oxide and promotes the performance of the cement-based adsorbentThe oxygen-containing group is enhanced.
Adding 1g of cement-based adsorbent into 100mL of copper ion-containing solution, adjusting the pH value of the solution to 6 at the constant temperature of 25 +/-0.5 ℃, oscillating (150 revolutions per minute) for 2 hours, and measuring that the final equilibrium adsorption rate of the cement-based adsorbent to the copper ions in the solution is 99.587% and the adsorption capacity is 8.166 mg/g.
Example 3
Ball-milling the fly ash on a ball mill for 2 hours at the rotating speed of 300r/min, and then sieving the fly ash with a 80-mesh sieve to obtain fly ash powder; 9g of fly ash powder is mixed with 2.5moL/LCa (OH)2Stirring the solution for 30min in a water bath at 90 ℃ at the rotating speed of 300r/min according to the dosage ratio of 1g to 5mL, then carrying out centrifugal separation, washing with water to be neutral, drying, grinding and sieving with a 100-mesh sieve to obtain modified fly ash;
Weighing 1.5g of graphene oxide, adding the graphene oxide into 11mL of distilled water, performing ultrasonic treatment for 2 hours to obtain a uniformly dispersed graphene oxide suspension, mixing the graphene oxide suspension with a 2mLPCAQ8081 polycarboxylate superplasticizer, and stirring for 20 minutes at 35 ℃ at 200r/min to obtain a graphene oxide/polycarboxylate superplasticizer mixed solution;
Weighing 10g of cement and the obtained modified fly ash into a stirrer, sequentially adding 7mL of graphene oxide/polycarboxylic acid water reducer mixed solution and 0.6mL of sodium dodecyl benzene sulfonate foaming agent, stirring for 1min at a stirring speed of 30r/min, then adding 6mL of graphene oxide/polycarboxylic acid water reducer mixed solution, stirring for 1min at a stirring speed of 30r/min, stopping for 2min, stirring for 5min at a stirring speed of 100r/min, then placing into a mold, compacting, leveling, maintaining for 7 days at 20 ℃ under the condition that the relative humidity is 98% until forming, finally grinding into powder, and sieving with a 60-mesh sieve to obtain the cement-based adsorbent.
Adding 1g of cement-based adsorbent into 100mL of copper-ion-containing solution, adjusting the pH value of the solution to 6 under the condition of constant temperature of 25 +/-0.5 ℃, respectively oscillating (150 revolutions per minute) for 5min, 10min, 30min, 1h, 2h, 6h, 12h, 24h and 48h, separating and filtering, measuring the concentration of the residual copper ions in the solution, and measuring the final equilibrium adsorption rate of the cement-based adsorbent to the copper ions in the solution to be 57.261%, 59.279%, 66.708%, 88.443%, 98.0922%, 99.5797%, 99.589%, 99.833% and 99.938% in sequence, wherein the adsorption amounts are 4.719mg/g, 4.885mg/g, 5.497mg/g, 7.289mg/g, 8.084mg/g, 8.206mg/g, 8.207mg/g, 8.227mg/g and 8.236mg/g in sequence.
FIG. 4 is a graph showing the relationship between the adsorption effect of the cement-based adsorbent prepared in example 3 on copper ions and the adsorption time, and it can be seen that the cement-based adsorbent can adsorb Cu ions within 0-120 min2+The adsorption rate of (a) is fast and shows a straight-line rise, which is mainly caused by surface diffusion and chemical reaction. This is due to the Cu in the initial solution2+The concentration difference promotes the transfer to the surface of the cement-based adsorbent, and the Cu occupying the surface active sites of the cement-based adsorbent2+The chemical reaction with the oxygen-containing functional group such as a hydroxyl group, a carboxyl group, and an epoxy group in the cement-based adsorbent further accelerates the increase of the adsorption rate. With the increase of the adsorption time, the adsorption quantity does not change greatly and shows a gentle trend of a straight line shape, which indicates that the surface active sites of the cement-based adsorbent are close to saturation, and the Cu is close to saturation2+Slowly migrates to the internal active sites and the adsorption gradually approaches equilibrium.
Table 1 example 3 cement-based sorbent prepared versus Cu2+Adsorption kinetics fitting parameters of
From Table 1, the correlation coefficient R of the quasi-second order kinetic model20.84697, significantly higher than the quasi-first order kinetic model (R)20.62671) and the maximum adsorption quantity (Qe-8.1168 mg/g) obtained by the quasi-two-stage kinetic model is more consistent with the maximum adsorption quantity (Qe-8.2070 mg/g) under the experimental condition, which indicates that the cement-based adsorbent has Cu adsorption2+The adsorption process follows a quasi-second-order kinetic model, the adsorption speed control step is mainly chemical adsorption, and the driving force of the adsorption reaction mainly comes from the chemical reaction.
adding 1g of cement-based adsorbent into 100mL of copper ion-containing solution, adjusting the concentration of copper ions to 82.409mg/L, adjusting the pH value of the solution to 6, oscillating (150 revolutions per minute) for 1h at 25 ℃, 40 ℃ and 60 ℃ respectively, separating and filtering, and measuring the concentration of the residual copper ions in the solution.
FIG. 5 is a graph of the adsorption effect of the cement-based adsorbent prepared in example 3 on copper ions versus temperature, and it can be seen from the graph that the adsorption amount of the cement-based adsorbent on copper is increased with the temperature, which shows that the temperature rise is favorable for the cement-based adsorbent to adsorb Cu ions2+Also illustrates the adsorption of Cu by the cement-based adsorbent2+Is an endothermic process.
Adding 1g of cement-based adsorbent into 100mL of copper-ion-containing solution respectively, wherein the concentrations of the solutions are 44.886mg/L, 82.409mg/L, 145.211mg/L, 191.319mg/L and 286.131mg/L respectively, adjusting the pH value of the solution to be 6 under the condition of constant temperature of 25 +/-0.5 ℃, oscillating (150 revolutions per minute) for 2 hours, separating and filtering, measuring the concentration of the residual copper ions in the solution, and measuring the final equilibrium adsorption rates of the cement-based adsorbent to the copper ions in the solution to be 99.836%, 99.833%, 99.656%, 99.511% and 90.755% in sequence, wherein the adsorption amounts are 4.481mg/g, 8.227mg/g, 14.450mg/g, 19.038mg/g and 25.955mg/g in sequence.
FIG. 6 is a graph of the adsorption isotherm of copper ions by the cement-based adsorbent prepared in example 3; table 2 shows the parameters of the cement-based adsorbent to copper ion adsorption isotherm equation fitting. As shown in FIG. 6 and Table 2, the Langmuir model curve has better conformity with the experimental data and the correlation coefficient (R)20.9907) is significantly larger than Freundlich model (R)20.9566) to illustrate that the Langmuir model is more suitable for describing cement-based sorbents on Cu2+Also indicates that the adsorption behavior belongs to monolayer adsorption. Cement-based sorbent on Cu, available from Langmuir model2+The maximum adsorption amount of the adsorbent reaches 28.490mg/g, which is similar to the maximum adsorption amount of 25.9548mg/g measured under the experimental conditions. Compared with pyrophyllite (20.73mg/g) and sodium-based montmorillonite (23.73mg/g) in the prior art (see' Shinieng, Chengal, Liyunephelin, Broussonetia, sodium-based montmorillonite and pyrophyllite adsorption research in aqueous solution [ J]Guangzhou chemical, 2019,47(04):51-54. "), and bauxite of Liu Wen gang (2.837mg/g) (see" Liu Wen gang, Jiani, Zhanginfluence of Mingyu high-temperature roasting on adsorption performance of heavy metals in bauxite tailings [ J]Mineral product protection and utilization, 2017(06):93-96. ") adsorbent adsorption capacity, which indicates that the cement-based adsorbent provided by the invention is an adsorbent with stable adsorption performance and high efficiency.
Table 2 example 3 cement-based sorbent prepared versus Cu2+adsorption isotherm equation fitting parameters of
Adding 1g of cement-based adsorbent into 100mL of copper ion-containing solution, wherein the concentration of copper ions is 82.409mg/L, adjusting the pH values of the solution to be 2, 4, 6 and 8 respectively at the constant temperature of 25 +/-0.5 ℃, oscillating (150 revolutions per minute) for 2 hours, separating and filtering, and measuring the concentration of the remaining copper ions in the solution.
FIG. 7 is a graph showing the pH dependence of the adsorption effect of the cement-based adsorbent prepared in example 3 on copper ions, and it can be seen from the graph that the pH value is higher than that of Cu2+The influence of adsorption is large. When the pH value in the solution is increased from 2 to 6, Cu2+the adsorption amount of (A) was increased from 6.0141mg/g to 8.227 mg/g. This is due to the fact that as the pH increases, H in solution+Decrease in concentration, resulting in H+And Cu2+The mutual competition is weakened, the adsorption sites and functional groups on the surface of the cement-based adsorbent are exposed, thereby being beneficial to Cu2+Adsorption of (3); when the pH is higher>6 th, Cu2+The adsorption amount of (2) is rather decreased with the increase of pH value, because when pH is increased>6 th, Cu2+Hydrolysis begins, forming the complex Cu (OH)+Production of Cu (OH)2Precipitates, and the insoluble precipitates can be deposited on the surface of the cement-based adsorbent, occupy the adsorption sites of the cement-based adsorbent and interfere with functional groups and Cu2+Thereby reducing Cu2+The adsorption effect of (1).
the mechanical properties of the cement-based adsorbents prepared in examples 1 to 3 and the mechanical properties of conventional commercial cement were tested according to the test method of GB/T17617-2007, and the test results are shown in Table 3.
Table 3 mechanical properties of the cement-based adsorbents prepared in examples 1 to 3 and the mechanical property test results of the comparative examples
| Flexural strength (MPa) | Compressive strength (MPa) | |
| Comparative example | 4.89 | 32.78 |
| Example 1 | 7.61 | 41.65 |
| Example 2 | 8.13 | 45.87 |
| Example 3 | 8.87 | 48.35 |
The experimental results show that the cement is modified by adding the fly ash and the graphene oxide, so that the flexural strength and the compressive strength of the cement-based adsorbent are effectively enhanced, and the durability of the cement-based adsorbent is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The cement-based adsorbent is characterized by being prepared from the following components in parts by weight:
8-15 parts of cement, 5-12 parts of fly ash powder, 1.5-16 parts of calcium hydroxide, 0.1-2 parts of graphene oxide powder, 0.5-3 parts of polycarboxylic acid water reducing agent, 0.3-1 part of foaming agent and 25-87 parts of water.
2. The cement-based sorbent according to claim 1, wherein the fly ash powder has a particle size < 200 mesh.
3. The cement-based sorbent according to claim 1, wherein the graphene oxide powder has a particle size <120 mesh.
4. The cement-based sorbent according to claim 1, wherein the active content of the foaming agent is not less than 30%.
5. The method according to claim 1, wherein the Ca (OH)2The calcium hydroxide solution is added in a form of calcium hydroxide solution, and the molar concentration of the calcium hydroxide solution is 1-3 moL/L.
6. The method for preparing the cement-based adsorbent according to any one of claims 1 to 5, characterized by comprising the steps of:
mixing fly ash powder with Ca (OH)2Mixing the solutions, and carrying out modification reaction to obtain modified fly ash;
And mixing the modified fly ash, the graphene oxide powder, the polycarboxylic acid water reducing agent, the cement, the foaming agent and water, and then maintaining to obtain the cement-based adsorbent.
7. The preparation method according to claim 6, wherein the temperature of the modification reaction is 80 to 100 ℃ and the time is 30 to 60 min.
8. The preparation method according to claim 6, wherein the curing temperature is 18-22 ℃, the relative humidity is not less than 95 ℃, and the curing time is 3-7 days.
9. The application of the cement-based adsorbent described in any one of claims 1 to 5 or the cement-based adsorbent prepared by the preparation method described in any one of claims 6 to 8 in treating copper ion-containing solution.
10. The use according to claim 9, wherein the pH of the copper ion-containing solution is 2 to 8 and the concentration of copper ions is 50 to 500 mg/L.
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